Bleaching compounds comprising acyl valerolactam bleach activators

ABSTRACT

Laundry detergents and bleaching systems comprising acyl verolactam bleach activators having the formula: ##STR1## wherein R 1  is a substituted or unsubstituted alkyl or alkoxy group containing from about 1 to about 18 carbon atoms wherein the longest linear alkyl or alkoxy chain extending from and including the carbonyl carbon contains from about 2 to about 12 carbon atoms; ##STR2## wherein R 2 , R 3 , R 4 , R 5 , and R 6  are members selected from the group consisting of H, halogen, nitro, alkyl, alkoxy, alkoxyaryl, alkaryl, and alkaryloxy moieties containing from about 1 to about 12 carbon atoms, and substituents having the structures: ##STR3## wherein R 7  is selected from the group consisting of H, alkyl, alkaryl, alkoxy, alkoxyaryl, alkaryloxy, and aminoalkyl; X is O, NH, or NR 9 , wherein R 9  is H or a C 1  -C 4  alkyl group; and R 8  is an alkyl, cycloalkyl, or aryl group containing from 3 to 11 carbon atoms; or 
     c) mixtures of a) and b) 
     are provided. The bleach activators are effective under mixed soil conditions, especially mixtures of hydrophobic and hydrophilic soils and stains.

This is a continuation of application Ser. No. 08/082,207, filed on Jun.24, 1993, now U.S. Pat. No. 5,405,413.

FIELD OF THE INVENTION

The present invention relates to laundry detergents and bleachingsystems which comprise acyl valerolactam bleach activators.

BACKGROUND OF THE INVENTION

It has long been known that peroxygen bleaches are effective for stainand/or soil removal from fabrics, but that such bleaches are temperaturedependent. At a laundry liquor temperature of 60° C., peroxygen bleachesare only partially effective. As the laundry liquor temperature islowered below 60° C., peroxygen bleaches become relatively ineffective.As a consequence, there has been a substantial amount of industrialresearch to develop bleaching systems which contain an activator thatrenders peroxygen bleaches effective at laundry liquor temperaturesbelow 60° C.

Numerous substances have been disclosed in the art as effective bleachactivators. One widely-used bleach activator is tetraacetyl ethylenediamine (TAED). TAED provides effective hydrophilic cleaning especiallyon beverage stains, but has limited performance on dingy stains and bodysoils. Another type of activator, such as nonanoyloxybenzenesulfonate(NOBS) and other activators which generally comprise long chain alkylmoieties, is hydrophobic in nature and provides excellent performance ondingy stains. However, many of the hydrophobic activators developed thusfar can promote damage to natural rubber parts used in certain washingmachines and to natural rubber articles exposed to the activators.Because of these negative effects on natural rubber machine pans andarticles, the selection of such detergent-added bleaching systems hasbeen limited.

It has now been determined that in conventional bleaching systems,particularly those comprising a hydrophobic bleach activator and asource of hydrogen peroxide, the bleach activator undergoesperhydrolysis to form a peroxyacid bleaching agent. A by-product of theperhydrolysis reaction between such bleach activators and hydrogenperoxide is a diacylperoxide (DAP) species. It has now further beendiscovered that the DAP's derived from hydrophobic activators tend to beinsoluble, poorly dispersible, oily materials which form a residue whichcan deposit on the natural rubber machine parts that are exposed to thelaundry liquor. The oily DAP residue can form a film on the naturalrubber parts and promote free radical and peroxide damage to the rubber,which eventually leads to failure of the part. This, is particularlytrue of rubber parts which have prolonged exposure to the laundryliquor, such as sump hoses.

By the present invention, is has now been discovered that the class ofbleach activators derived from acyl valerolactams forms peroxyacids uponperhydrolysis without the production of oily, harmful DAP's. Withoutintending to be limited by theory, it is believed that the bleachactivators employed herein provide good cleaning performance with safetyto natural rubber, since they do not expose the natural rubber machineparts or articles to DAP oxidation. Whatever the reason, natural rubberparts and articles remain substantially undamaged by the bleachingsystems of the present invention.

By the present invention, it has also now been discovered the bleachactivators of this invention provide dingy soil clean-up and enhancednucleophilic and body soil removal. Furthermore, the bleaching systemsand activators herein are effective at low concentration levels and attemperatures below 60° C. when used in the manner provided by thisinvention. In addition, the activators herein have better perhydrolysisspeed and yield when compared to other lactam bleach activators, such asacyl caprolactam activators.

Accordingly, the present invention presents an effective, color-safebleaching system which does not promote damage to natural rubber partsin washing machines or damage to natural rubber articles.

SUMMARY OF THE INVENTION

The present invention relates to acyl valerolactam bleach activators andtheir use in bleaching systems and laundry detergents. The valerolactamsare selected from the group consisting of:

a) ##STR4## wherein R¹ is a substituted or unsubstituted, includingsaturated or unsaturated, alkyl or alkoxy group containing from about 1to about 18 carbon atoms wherein the longest linear alkyl or alkoxychain extending from and including the carbonyl carbon contains fromabout 2 to about 12 carbon atoms;

b) ##STR5## i.e., substituted and unsubstituted benzoyl valerolactamswherein substituents R², R³, R⁴, R⁵, and R⁶ are members selected fromthe group consisting of H, halogen, alkyl, alkoxy, alkoxyaryl, alkaryl,and alkaryloxy moieties having from about 1 to about 12 carbon atoms,preferably from about 3 to about 12 carbon atoms, and substituentshaving the structure: ##STR6## wherein R⁷ is selected from the groupconsisting of H, alkyl, alkaryl, alkoxy, alkoxyaryl, alkaryloxy, andaminoalkyl; X is O, NH or NR⁹, wherein R⁹ is H or a C₁ -C₄ alkyl group;R⁸ is an alkyl, cycloalkyl, or aryl group containing from 3 to 11 carbonatoms; and

c) mixtures of a) and b).

In a preferred embodiment of structure a), R¹ is selected from the groupconsisting of alkyl or alkoxy units having from about 7 to about 11carbon atoms, including heptyl, octyl, nonyl, decyl, undecyl, decenyl,2,4,4-trimethylpentyl, 1-ethylpentyl, and mixtures thereof.

In a preferred embodiment of structure b), R², R³, R⁴, and R⁵ are H andR⁶ is selected from the group consisting of H, methyl, methoxy, ethyl,ethoxy, propyl, propoxy, isopropyl, isopropoxy, butyl, tert-butyl,butoxy, tert-butoxy, pentyl, pentoxy, hexyl, hexoxy, Cl, and NO₂. Instill another preferred embodiment, R², R³, R⁴ are H, and R⁵ and R⁶ aremembers selected from the group consisting of methyl, methoxy, and Cl.

The invention also relates to bleaching systems and laundry detergentscomprising the bleach activators. Said bleaching system comprises:

A) at least about 0.1%, preferably from about 1% to about 75%, by weightof bleaching system, of a peroxygen bleaching compound capable ofyielding hydrogen peroxide in an aqueous solution;

B) at least about 0.1%, preferably from about 0.1% to about 50%, byweight, of one or more acyl valerolactam bleach activators selected fromthe group consisting of:

a) ##STR7## wherein R¹ is as defined above; b) ##STR8## wherein R², R³,R⁴, R⁵, and R⁶ are as defined above; and

c) mixtures of a) and b).

The peroxygen bleaching compound can be any peroxide source, and ispreferably a member selected from the group consisting of sodiumperborate monohydrate, sodium perborate tetrahydrate, sodiumpyrophosphate peroxyhydrate, urea peroxyhydrate, sodium percarbonate,sodium peroxide and mixtures thereof. Highly preferred peroxygenbleaching compounds are selected from the group consisting of sodiumperborate monohydrate, sodium perborate tetrahydrate, sodiumpercarbonate and mixtures thereof. The most highly preferred peroxygenbleaching compound is sodium percarbonate.

The invention also encompasses laundry compositions in granular, paste,liquid, or bar form which comprise at least about 0.1% of the aforesaidbleaching system together with at least about 1% of conventionaldetergent ingredients which are present in the composition at the levelsindicated hereinafter.

The acyl valerolactams herein can also be used in combination with otherbleach activators, such as N-acyl caprolactams, tetraacetyl ethylenediamine, alkanoxybenzenesulfonates, includingnonanoyloxybenzenesulfonate, benzoxazin-type bleach activators, andperoxyacid agents and activators having amide moieties. Preferably, ifusing an automatic washing machine equipped with natural rubber parts orif washing articles comprising natural rubber, the amount ofalkanoxybenezenesulfonates used in combination with the activators ofthis invention should be kept at a minimum.

The bleaching method herein is preferably conducted with agitation ofthe fabrics with an aqueous liquor containing the aforesaid bleachingsystem at levels from about 50 ppm to about 27,500 ppm. The method canbe carried out at any desired washing temperature, even at temperaturesbelow about 60° C., and is readily conducted at temperatures in therange of from about 5° C. to about 45° C. The method can be conductedconveniently using a composition which is in bar form, but can also beconducted using granules, flakes, powders, pastes, liquids and the like.

The aqueous laundry liquor typically comprises at least about 300 ppm ofconventional detergent ingredients, as well as at least about 25 ppm ofthe bleaching compound and at least about 25 ppm of the bleachactivator. Preferably, the liquor comprises from about 900 ppm to about20,000 ppm of conventional detergent ingredients, from about 100 ppm toabout 25,000 ppm of the bleaching compound and from about 100 ppm toabout 2,500 ppm of the bleach activator. The conventional detergentingredients and bleaching system will typically be combined into adetergent composition such as a granular laundry detergent or laundrydetergent bar.

The conventional detergent ingredients employed in said method and inthe compositions herein comprise from about 1% to about 99.8%,preferably from about 5% to about 80%, of a detersive surfactant.Optionally, the detergent ingredients comprise from about 5% to about80% of a detergent builder. Other optional detersive adjuncts can alsobe included in such compositions at conventional usage levels.

All percentages, ratios, and proportions herein are by weight, unlessotherwise specified. All documents cited are incorporated herein byreference.

DETAILED DESCRIPTION OF THE INVENTION

The bleaching system employed in the present invention provideseffective and efficient surface bleaching of fabrics which therebyremoves stains and/or soils from the fabrics. The bleaching system isparticularly efficient at cleaning concentrated soil loads, especiallymixtures of hydrophobic and hydrophilic soils. Hydrophobic soils aregenerally associated with nucleophilic, lipid and protein-based soilsand stains, such as body soils, blood, etc., but are also effective onso-called "dingy soils". Dingy soils are those that build up on textilesafter numerous cycles of usage and washing, and result in a gray oryellow tint on white fabrics. Hydrophilic soils include food andbeverage stains. Further, the bleaching system is safe to natural rubbermachine parts and articles.

The bleaching mechanism and, in particular, the surface bleachingmechanism are not completely understood. However, it is generallybelieved that the bleach activator undergoes nucleophilic attack by aperhydroxide anion, which is generated from the hydrogen peroxideevolved by the peroxygen bleaching compound, to form a peroxycarboxylicacid. This reaction is commonly referred to as perhydrolysis. It is alsobelieved, that the bleach activators within this invention can renderperoxygen bleaches more efficient even at laundry liquor temperatureswherein bleach activators are not necessary to activate the bleach,i.e., above about 60° C. Therefore, with bleach systems of theinvention, less peroxygen bleach is required to achieve the same levelof surface bleaching performance as is obtained with the peroxygenbleach alone.

The components of the bleaching system herein comprise the bleachactivator and the peroxide source, as described hereinafter.

Bleach Activators

Methods of making acyl valerolactams are illustrated by laboratorysyntheses included in Examples I and II.

Preferred valerolactams of structure a) include those wherein the R¹moiety is selected from alkyl and alkoxy groups containing from about 7to about 11 carbon atoms. Examples of preferred valerolactams includeoctanoyl valerolactam, nonanoyl valerolactam, decanoyl valerolactam,undecenoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam,2-ethylhexanoyl valerolactam, isononanoyl valerolactam and mixturesthereof. Highly preferred valerolactams of structure a) include nonanoylvalerolactam, isononanoyl valerolactam, and 2-ethyhexanoyl valerolactam.

Preferred valerolactams of structure b) include benzoyl valerolactam,substituted benzoyl valerolactam, including alkaryl and alkoxyarylvalerolactams wherein the alkaryl or alkoxyaryl moiety contains fromabout 3 to about 12 carbon atoms, terephthaloyl divalerolactam, andmixtures thereof. Examples of substituted benzoyl valerolactams includemethylbenzoyl valerolactam, ethylbenzoyl valerolactam, ethoxybenzoylvalerolactam, propylbenzoyl valerolactam, propoxybenzoyl valerolactam,isopropylbenzoyl valerolactam, isopropoxybenzoyl valerolactam,butylbenzoyl valerolactam, butoxybenzoyl valerolactam, tertbutylbenzoylvalerolactam, tertbutoxybenzoyl valerolactam, pentylbenzoylvalerolactam, pentoxybenzoyl valerolactam, hexylbenzoyl valerolactam,hexoxybenzoyl valerolactam, 2, 4,6-trichlorobenzoyl valerolactam,pentafluorobenzoyl valerolactam, dichlorobenzoyl valerolactam,dimethoxybenzoyl valerolactam, 4-nitrobenzoyl valerolactam,3-chlorobenzoyl valerolactam, 4-chlorobenzoyl valerolactam,2,4-dichlorobenzoyl valerolactam, terephthaloyl divalerolactam, andmixtures thereof. Highly preferred valerolactams of structure b) includebenzoyl valerolactam, 3-chlorobenzoyl valerolactam, and 4- nitrobenzoylvalerolactam.

The bleaching system comprises at least about 0.1%, preferably fromabout 0.1% to about 50%, more preferably from about 1% to about 30%,most preferably from about 3% to about 25%, by weight, of one or moreacyl valerolactam bleach activators. In highly preferred embodiments,the bleaching system comprises percarbonate and a bleach activatorselected from the group consisting of benzoyl valerolactam, nonanoylvalerolactam, isononanoyl valerolactam, 2-ethylhexanoyl valerolactam,3-chlorobenzoyl valerolactam, and 4-nitrobenzoyl valerolactam.

When the activators are used, optimum surface bleaching performance isobtained with washing solutions wherein the pH of such solution isbetween about 7 and 10.5, preferably between about 8.5 and 10.5, mostpreferably about 9.5 to about 10.5, in order to facilitate theperhydrolysis reaction. Such pH can be obtained with substances commonlyknown as buffering agents, which are optional components of thebleaching systems herein.

The Peroxygen Bleaching Compound

The peroxygen bleaching compounds useful herein are those capable ofyielding hydrogen peroxide in an aqueous liquor. These compounds arewell known in the art and include hydrogen peroxide and the alkali metalperoxides, organic peroxide bleaching compounds such as urea peroxide,and inorganic persalt bleaching compounds, such as the alkali metalperborates, percarbonates, perphosphates, and the like. Mixtures of twoor more such bleaching compounds can also be used, if desired.

Preferred peroxygen bleaching compounds include sodium perborate,commercially available in the form of mono-, tri-, and tetra-hydrate,sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide,and sodium percarbonate. Particularly preferred are sodium perboratetetrahydrate, sodium perborate monohydrate and sodium percarbonate.Sodium percarbonate is especially preferred because it is very stableduring storage and yet still dissolves very quickly in the bleachingliquor. It is believed that such rapid dissolution results in theformation of higher levels of percarboxylic acid and, thus, enhancedsurface bleaching performance.

Highly preferred percarbonate can be in uncoated or coated form. Theaverage particle size of uncoated percarbonate ranges from about 400 toabout 1200 microns, most preferably from about 400 to about 600 microns.If coated percarbonate is used, the preferred coating materials includemixtures of carbonate and sulphate, silicate, borosilicate, or fattycarboxylic acids.

The bleaching system comprises at least about 0.1%, preferably fromabout 1% to about 75%, more preferably from about 3% to about 40%, mostpreferably from about 3% to about 25%, by weight, of said peroxygenbleaching compound capable of yielding hydrogen peroxide in an aqueoussolution.

The weight ratio of bleach activator to peroxygen bleaching compound inthe bleaching system typically ranges from about 2:1 to 1:5. Inpreferred embodiments, the ratio ranges from about 1:1 to about 1:3.

The bleach activator/bleaching compound systems herein are useful per seas bleaches. However, such bleaching systems are especially useful incompositions which can comprise various detersive adjuncts such assurfactants, builders, enzymes, and the like as disclosed hereinafter.Such laundry detergent compositions comprise at least about 0.1%,preferably from about 1% to about 50%, of the bleaching system and atleast about 1%, preferably from about 50% to about 99.9%, ofconventional detergent ingredients.

Detersive Surfactant

The amount of detersive surfactant included in the fully formulateddetergent compositions afforded by the present invention can vary fromabout 1% to about 99.8%, by weight of the detergent ingredients,depending upon the particular surfactants used and the effects desired.Preferably, the detersive surfactants comprise from about 5% to about80%, by weight of the detergent ingredients.

The detersive surfactant can be nonionic, anionic, ampholytic,zwitterionic, or cationic. Mixtures of these surfactants can also beused. Preferred detergent compositions comprise anionic detersivesurfactants or mixtures of anionic surfactants with other surfactants,especially nonionic surfactants.

Nonlimiting examples of surfactants useful herein include theconventional C₁₁ -C₁₈ alkyl benzene sulfonates and primary, secondary,and random alkyl sulfates, the C₁₀ -C₁₈ alkyl alkoxy sulfates, the C₁₀-C₁₈ alkyl polyglycosides and their corresponding sulfatedpolyglycosides, C₁₂ -C₁₈ alpha-sulfonated fatty acid esters, C₁₂ -C₁₈alkyl and alkyl phenol alkoxylates (especially ethoxylates and mixedethoxy/propoxy), C₁₂ -C₁₈ betaines and sulfobetaines ("sultaines"), C₁₀-C₁₈ amine oxides, and the like. Other conventional useful surfactantsare listed in standard texts.

One particular class of adjunct nonionic surfactants especially usefulherein comprises the polyhydroxy fatty acid amides of the formula:##STR9## wherein: R¹ is H, C₁ -C₈ hydrocarbyl, 2-hydroxyethyl,2-hydroxypropyl, or a mixture thereof, preferably C₁ -C₄ alkyl, morepreferably C₁ or C₂ alkyl, most preferably C₁ alkyl (i.e., methyl); andR² is a C₅ -C₃₂ hydrocarbyl moiety, preferably straight chain C₇ -C₁₉alkyl or alkenyl, more preferably straight chain C₉ -C₁₇ alkyl oralkenyl, most preferably straight chain C₁₁ -C₁₉ alkyl or alkenyl, ormixture thereof; and Z is a polyhydroxyhydrocarbyl moiety having alinear hydrocarbyl chain with at least 2 (in the case of glyceraldehyde)or at least 3 hydroxyls (in the case of other reducing sugars) directlyconnected to the chain, or an alkoxylated derivative (preferablyethoxylated or propoxylated) thereof. Z preferably will be derived froma reducing sugar in a reductive amination reaction; more preferably Z isa glycityl moiety. Suitable reducing sugars include glucose, fructose,maltose, lactose, galactose, mannose, and mannose, as well asglyceraldehyde. As raw materials, high dextrose corn syrup, highfructose corn syrup, and high maltose corn syrup can be utilized as wellas the individual sugars listed above. These corn syrups may yield a mixof sugar components for Z. It should be understood that it is by nomeans intended to exclude other suitable raw materials. Z preferablywill be selected from the group consisting of --CH₂ --(CHOH)_(n) --CH₂OH, --CH(CH₂ OH)--(CHOH)_(n--1) --CH₂₀ H, --CH₂ --(CHOH)₂(CHOR')(CHOH)--CH₂ OH, where n is an integer from 1 to 5, inclusive, andR' is H or a cyclic mono- or poly- saccharide, and alkoxylatedderivatives thereof. Most preferred are glycitals wherein n is 4,particularly --CH₂ --(CHOH)₄ --CH₂ OH.

In Formula (I), R¹ can be, for example, N-methyl, N-ethyl, N-propyl,N-isopropyl, N-butyl, N-isobutyl, N-2-hydroxy ethyl, or N-2-hydroxypropyl. For highest sudsing, R¹ is preferably methyl or hydroxyalkyl. Iflower sudsing is desired, R¹ is preferably C₂ -C₈ alkyl, especiallyn-propyl, iso-propyl, n-butyl, iso-butyl, pentyl, hexyl and 2-ethylhexyl.

R² --CO--N<can be, for example, cocamide, stearamide, oleamide,lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.

Detergent Builders

Optional detergent ingredients employed in the present invention containinorganic and/or organic detergent builders to assist in mineralhardness control. If used, these builders comprise from about 5% toabout 80% by weight of the detergent compositions.

Inorganic detergent builders include, but are not limited to, the alkalimetal, ammonium and alkanolammonium salts of polyphosphates (exemplifiedby the tripolyphosphates, pyrophosphates, and glassy polymericmeta-phosphates), phosphonates, phytic acid, silicates, carbonates(including bicarbonates and sesquicarbonates), sulphates, andaluminosilicates. However, non-phosphate builders are required in somelocales.

Examples of silicate builders are the alkali metal silicates,particularly those having a SiO₂ :Na₂ O ratio in the range 1.6:1 to3.2:1 and layered silicates, such as the layered sodium silicatesdescribed in U.S. Pat. No. 4,664,839, issued May 12, 1987 to H. P.Rieck, available from Hoechst under the trademark "SKS"; SKS-6 is anespecially preferred layered silicate builder.

Carbonate builders, especially a finely ground calcium carbonate withsurface area greater than 10 m² /g, are preferred builders that can beused in granular compositions. The density of such alkali metalcarbonate built detergents can be in the range of 450-850 g/l with themoisture content preferably below 4%. Examples of carbonate builders arethe alkaline earth and alkali metal carbonates as disclosed in GermanPatent Application No. 2,321,001 published on Nov. 15, 1973.

Aluminosilicate builders are especially useful in the present invention.Preferred aluminosilicates are zeolite builders which have the formula:

    Na.sub.z  (AlO.sub.2).sub.z (SiO.sub.2).sub.y !·xH.sub.2 O

wherein z and y are integers of at least 6, the molar ratio of z to y isin the range from 1.0 to about 0.5, and x is an integer from about 15 toabout 264.

Useful aluminosilicate ion exchange materials are commerciallyavailable. These aluminosilicates can be crystalline or amorphous instructure and can be naturally-occurring aluminosilicates orsynthetically derived. A method for producing alumino-silicate ionexchange materials is disclosed in U.S. Pat. No. 3,985,669, Krummel, etal, issued Oct. 12, 1976. Preferred synthetic crystallinealuminosilicate ion exchange materials useful herein are available underthe designations Zeolite A, Zeolite P (B), and Zeolite X. Preferably,the aluminosilicate has a particle size of about 0.1-10 microns indiameter.

Organic detergent builders suitable for the purposes of the presentinvention include, but are not restricted to, a wide variety ofpolycarboxylate compounds, such as ether polycarboxylates, includingoxydisuccinate, as disclosed in Berg U.S. Pat. No. 3,128,287, issuedApr. 7, 1964, and Lamberti et al, U.S. Pat. No. 3,635,830, issued Jan.18, 1972. See also "TMS/TDS" builders of U.S. Pat. No. 4,663,071, issuedto Bush et al, on May 5, 1987.

Other useful detergent builders include the etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene orvinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonicacid, and carboxymethyloxysuccinic acid, the various alkali metal,ammonium and substituted ammonium salts of polyacetic acids such asethylenediamine tetraacetic acid and nitrilotriacetic acid, as well aspolycarboxylates such as mellitic acid, succinic acid, oxydisuccinicacid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof(particularly sodium salt), are preferred polycarboxylate builders thatcan also be used in granular compositions, especially in combinationwith zeolite and/or layered silicate builders.

Also suitable in the detergent compositions of the present invention arethe 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compoundsdisclosed in U.S. Pat. No. 4,566,984, Bush, issued Jan. 28, 1986.

In situations where phosphorus-based builders can be used, andespecially in the formulation of bars used for hand-launderingoperations, the various alkali metal phosphates such as the well-knownsodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphatecan be used. Phosphonate builders such asethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see,for example, U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148and 3,422,137) can also be used.

Optional Detersive Adjuncts

As a preferred embodiment, the conventional detergent ingredientsemployed herein can be selected from typical detergent compositioncomponents such as detersive surfactants and detergent builders.Optionally, the detergent ingredients can include one or more otherdetersive adjuncts or other materials for assisting or enhancingcleaning performance, treatment of the substrate to be cleaned, or tomodify the aesthetics of the detergent composition. Usual detersiveadjuncts of detergent compositions include the ingredients set forth inU.S. Pat. No. 3,936,537, Baskerville et al. Adjuncts which can also beincluded in detergent compositions employed in the present invention, intheir conventional art-established levels for use (generally from 0% toabout 20% of the detergent ingredients, preferably from about 0.5% toabout 10%), include enzymes, especially proteases, lipases andcellulases, color speckles, suds boosters, suds suppressors, antitarnishand/or anticorrosion agents, soil-suspending agents, soil releaseagents, dyes, fillers, optical brighteners, germicides, alkalinitysources, hydrotropes, antioxidants, enzyme stabilizing agents, perfumes,solvents, solubilizing agents, clay soil removal/anti-redepositionagents, polymeric dispersing agents, processing aids, fabric softeningcomponents such as smectite clays, static control agents, etc.

Bleach systems optionally, but preferably, will also comprise a chelantwhich not only enhances bleach stability by scavenging heavy metal ionswhich tend to decompose bleaches, but also assists in the removal ofpolyphenolic stains such as tea stains, and the like. Various chelants,including the aminophosphonates, available as DEQUEST from Monsanto, thenitrilotriacetates, the hydroxyethyl-ethylenediamine triacetates, andthe like, are known for such use. Preferred biodegradable,non-phosphorus chelants include ethylenediamine disuccinate ("EDDS"; seeU.S. Pat. No. 4,704,233, Hartman and Perkins),ethylenediamine-N,N'-diglutamate (EDDG) and2-hydroxypropylenediamine-N,N'-disuccinate (HPDDS) compounds. Suchchelants can be used in their alkali or alkaline earth metal salts,typically at levels from about 0.1% to about 10% of the presentcompositions.

Optionally, the detergent compositions employed herein can comprise, inaddition to the bleaching system of the present invention, one or moreother conventional bleaching agents, activators, or stabilizers. Ingeneral, the formulator will ensure that the bleach compounds used arecompatible with the detergent formulation. Conventional tests, such astests of bleach activity on storage in the presence of the separate orfully-formulated ingredients, can be used for this purpose.

Specific examples of optional bleach activators for incorporation inthis invention include tetraacetyl ethylene diamine (TAED), N-acylcaprolactams, alkanoyloxybenzenesulfonates, includingnonanoyloxybenzenesulfonate and benzoyloxybenzenesulfonate, thebenzoxazin-type bleaching activators disclosed in U.S. Pat. No.4,966,723, Hodge et al, issued Oct. 30, 1990, and the peroxyacid agentsand activators having amide moieties disclosed in U.S. Pat. No.4,634,551, Bums et al, issued Jan. 6, 1987. Such bleaching compounds andagents can be optionally included in detergent compositions in theirconventional an-established levels of use, generally from 0% to about15%, by weight of detergent composition.

Bleaching activators of the invention are especially useful inconventional laundry detergent compositions such as those typicallyfound in granular detergents or laundry bars. U.S. Pat. No. 3,178,370,Okenfuss, issued Apr. 13, 1965, describes laundry detergent bars andprocesses for making them. Philippine Pat. No. 13,778, Anderson, issuedSept. 23, 1980, describes synthetic detergent laundry bars. Methods formaking laundry detergent bars by various extrusion methods are wellknown in the art.

Perhydrolysis Speed and Yield

The activators herein have better perhydrolysis speed and yield whencompared to other lactam derived bleach activators. For example, afterapproximately five minutes, a solution of nonanoyl valerolactamgenerates approximately 95% of the theoretical yield of peracid. Incomparison, after approximately five minutes, an identical solution ofnonanoyl caprolactam generates approximately 35% of the theoreticalyield of peracid. After 15 minutes, the nonanoyl caprolactam solutiongenerates approximately 68% of the theoretical yield of peracid.Accordingly, the user can expect better bleaching performance at shorterwash times with the valerolactam activators.

The comparison is made using standard peracid titration procedures. Theactivator is dispersed in a detergent solution. At specific timeintervals, samples of the solution are taken and added to a mixture ofacetic acid, water, and ice to quench the perhydrolysis reaction. Aquantity of potassium iodide is added to the sample giving the sample abrown color. The resulting solution is titrated with thiosulphate untilthe color is removed. From the known quantity of thiosulphate used inthe titration, the amount of peracid can be determined.

Liquid Bleaches

The bleach activators of this invention are also useful in liquid bleachcompositions. Therefore, in accordance with one aspect of the invention,a stable aqueous liquid bleach is provided. In a preferred embodiment,the liquid bleaches comprise a liquid valerolactam such as decanoylvalerolactam or nonanoyl valerolactam which is most preferablyemulsified in the peroxide liquid composition. Such liquid bleachescomprise:

A) from about 1% to about 25%, more preferably from about 3% to about12%, most preferably from about 5% to about 10%, by weight, of a (solidor, preferably, liquid) valerolactam bleach activator selected from thegroup consisting of:

a) ##STR10## wherein R₁ is as defined above; b) ##STR11## wherein R²,R³, R⁴, R⁵, and R⁶ are as defined above; and

c) mixtures of a) and b);

B) from about 0.1% to about 10%, more preferably from about 0.3% toabout 7%, most preferably from about 0.5% to about 5%, by weight, of aperoxygen bleaching compound comprising hydrogen peroxide or which iscapable of yielding hydrogen peroxide in an aqueous solution.

Optionally, the liquid bleach composition can further comprise fromabout 1% to about 20%, preferably from about 5% to about 15%, by weight,of a phase stabilizer and from about 0.001% to about 2%, preferably fromabout 0.05% to about 1%, by weight, of a chelating agent. The balance ofthe liquid bleach composition is water.

The liquid peroxide-containing bleach is formulated in the acid pH rangefor stability. In-use in a laundering operation, the bleach is added toa laundry liquor which typically has a pH in the base range, i.e.,9.5-13, which then destabilizes the peroxide to perform its bleachingfunction.

Nonionic Surfactant

The liquid bleach compositions of the invention, optionally, butpreferably, include a nonionic surfactant as a phase stabilizer tofacilitate maintenance of its continuous isotropic state. To this end,several nonionic surfactants are particularly useful. Suitable nonionicsurfactants include the polyethylene oxide condensates of alkyl phenols,e.g., the condensation products of alkyl phenols having an alkyl groupcontaining from about 6 to 15 carbon atoms, in either a straight chainor branched chain configuration, with from about 3 to 20 moles ofethylene oxide per mole of alkyl phenol.

Other nonionic surfactants which function as suitable phase stabilizersare the water-soluble and water-dispersible condensation products ofaliphatic alcohols o containing from 8 to 22 carbon atoms, in eitherstraight chain or branched configuration, with from 3 to 20 moles ofethylene oxide per mole of alcohol. Still other nonionic surfactantsinclude semi-polar nonionic surfactants such as water-soluble amineoxides containing one alkyl moiety of from about 10 to 18 carbon atomsand two moieties selected from about 1 to about 3 carbon atoms;water-soluble phosphine oxides containing one alkyl moiety of about 10to 18 carbon atoms and two moieties selected from the group consistingof alkyl groups and hydroxyalkyl groups containing fro about 1 to 3carbon atoms; and water-soluble sulfoxides containing only alkyl moietyof from about 10 to 18 carbon atoms and a moiety selected from the groupconsisting of alkyl and hydroxyalkyl moieties of from about 1 to 3carbon atoms.

Preferred nonionic surfactants are of the formula R¹ (OC₂ H₄)_(n) OH,wherein R¹ is a C₈ -C₁₆ alkyl group of C₈ -C₁₂ alkyl phenyl group, and nis from 3 to about 20. Particularly preferred are condensation productsof C₉ -C₁₅ alcohols with from about 5 to about 20 moles of ethyleneoxide per mole of alcohol. The most preferred nonionic of this type isan alkyl ethoxylate having from about 9 to 11 carbon atoms and anaverage degree of ethoxylation of about 10 which is available from ShellOil Co. under the product name of NEODOL 91-10.

The liquid bleach composition will generally comprise from about 1% toabout 20%, preferably from about 5% to about 15%, by weight, of thenonionic surfactant phase stabilizer.

With the aforementioned chelating agent and phase stabilizer, i.e.nonionic surfactant, the stable aqueous liquid bleach composition inaccordance with the invention can be produced. The resulting liquidbleach composition has a relatively low viscosity which renders it morepourable and therefore, more convenient for users especially when thecomposition is used as an additive. The viscosity of the present liquidbleach is preferably in a range from about 10 to about 500 cps, morepreferably from about 10 to about 300 cps, and most preferably fromabout 10 to 100 cps.

pH Adjusting Agent

It has been found that optimum stability of the liquid peroxygenbleaches is achieved when the aqueous liquid bleach has a pH in rangefrom about 2 to about 7, more preferably from about 3 to about 5, andmost preferably from about 3.5 to about 4.5. For purposes of achievingsuch pH's in the present stable aqueous liquid bleach composition, a pHadjusting agent may optionally be included. It is a well known techniqueto use pH adjusting agents to alter aqueous solutions such as thepresent liquid bleach, to the desired pH.

Typical pH adjusting agents can be either of the acid type or of thebase type. Acidic pH adjusting agents are designed to compensate for thepresence of other highly alkaline materials land include organic andinorganic acids, acid mixtures and acid salts. Non-limiting examples ofsuch acidic pH adjusting agents include citric acid, glycolic acid,phosphoric acid, lauric acid and mixtures thereof. Representativeexamples of alkaline pH adjusting agents include but not limited tosodium hydroxide, salts of phosphates, titrates and mixtures thereof

In addition to the materials described above, the liquid bleach may alsoinclude perfumes colorants, brighteners, viscosity adjusters such asthickeners, and other conventional components typically used indetergent compositions, if compatible.

The liquid bleach of the invention can be produced by a wide variety ofprocesses. While not intending to be limiting, the most economical andeasiest manner in which the liquid bleach can be produced is to simplydisperse all of the preferred components in water. As those skilled inthe art will appreciate, it may be desirable to disperse certaincomponents in water before others. This offers an inexpensive way toproduce the present liquid bleach composition.

In accordance with another aspect of the invention, a method ofbleaching fabrics comprises the step of contacting fabrics with adiluted aqueous solution of the liquid composition of the invention.Another method contemplated by the invention involves laundering soiledclothes, using the liquid bleach composition as an additive. The methodcomprises the steps of contacting fabrics with an effective amount of adetergent composition in combination with an effective amount of astable aqueous liquid bleach composition. In practicing these methods,the stable aqueous liquid bleach compositions of the present inventioncan be used in widely varying concentrations depending on the particularapplication involved but are generally utilized in an amount sufficientto provide from about 1.0 ppm to about 50 ppm available oxygen from theperacid in solution.

The following examples are given to further illustrate the presentinvention, but are not intended to be limiting thereof.

EXAMPLE I

Synthesis of benzoyl valerolactam--To a 500 ml flask equipped with areflux condenser, overhead stirrer, and addition funnel is charged 0.12moles of valerolactam, 0.15 moles of triethylamine and 150 ml oftoluene. The solution is heated to 80° C. and a solution of 0.12 molesof benzoyl chloride dissolved in 50 ml of toluene is added over 20minutes. The mixture is refluxed for six hours with stirring, cooled,and filtered. The filtrate is concentrated under vacuum to a brown solidwhich is recrystallized from toluene to yield 0.092 moles of benzyolvalerolactam. ¹ H NMR analysis shows the product to be greater than 95%pure. Analysis: ¹ H NMR (ppm)-1.9(M,4H); 2.5(t, 2H); 3.7(t,2H);7.4(M,5H). IR (cm¹) -2925, 2856, 1686, 1673, 1458, 1287.

EXAMPLE II

Synthesis of nonanoyl valerolactam-To a 5 liter flask equipped with areflux condenser, argon sweep, addition funnel, and overhead stirrer ischarged 2.5 moles of valerolactam, 2.75 moles of triethylamine, and 2liters of toluene. The solution is heated to reflux, and 2.5 moles ofnonanoyl chloride is added over 1.5 hours. The mixture is refluxed withstirring for 6 hours, cooled, and filtered. The filtrate is concentratedunder vacuum, and the resultant oil is distilled at 162° C. andapproximately 1 mm Hg to yield 1.6 moles of nonanoyl valerolactam. NMRanalysis shows the product to be greater than 95% pure. Analysis: ¹ HNMR (ppm)-0.9(t,3H); 1.3(M,10H); 1.6(M, 2H); 1.9(M,4H); 2.6(M,2H);2.9(t,2H); 3.7(M,2H). IR (cm¹) - 2927, 2857 1461, 1377, 1291, 1197,1161.

EXAMPLE III

A granular detergent composition is prepared comprising the followingingredients.

    ______________________________________    Component               Weight %    ______________________________________    C.sub.12 linear alkyl benzene sulfonate                            22    Phosphate (as sodium tripolyphosphate)                            20    Sodium carbonate        10    Sodium silicate         3    Sodium percarbonate*    20    Ethylenediamine disuccinate chelant (EDDS)                            0.4    Sodium sulfate          5.5    Nonanoyl valerolactam   10    Minors, filler** and water                            Balance to 100%    ______________________________________     *Average particle size of 400 to 1200 microns.     **Can be selected from convenient materials such as CaCO.sub.3, talc,     clay, silicates, and the like.

An aqueous crutcher mix of heat and alkali stable components of thedetergent composition is prepared and spray-dried. The other ingredientsare admixed therewith so that they contain the ingredients tabulated atthe levels shown.

The detergent granules with bleaching system are added together with a 6lb. (2.7 kg) load of fabrics to a Sears KENMORE washing machine. Actualweight of the detergent composition is taken to provide a 1500 ppmconcentration of the detergent composition in the 17 gallon (65 1)water-fill machine. The water used has 7 grains/gallon hardness and a pHof 7 to 7.5 prior to (about 9 to about 10.5 after) addition of thedetergent composition. The fabrics are laundered at 35° C. (95° F.) fora full cycle (12 min.) and rinsed at 21° C. (70° F.).

At the end of the last rinse cycle, the test swatches are dried in adryer. Tristimulus meter readings (L,a,b) are then determined for eachtest swatch. Whiteness performance in terms of Hunter Whiteness Values(W) is then calculated according to the following equation:

    W=(7L.sup.2 -40Lb)/700

The higher the value for W, the better the whiteness performance. In theabove test, fabrics exposed to the bleaching system displaysignificantly improved whiteness after laundering compared with fabricswhich have not been exposed to the bleaching system of the invention.

EXAMPLE IV

A granular detergent is prepared by a procedure identical to that ofExample HII with the exception that 20% benzoyl valerolactam issubstituted for the nonanoyl valerolactam bleach activator. Thelaundering method of Example III is repeated. In the test, all fabricsdisplay significantly improved whiteness after laundering compared withfabrics which have not been exposed to the bleaching system of theinvention.

EXAMPLE V

A granular detergent is prepared by a procedure identical to that ofExample III, with the exceptions that 10% 4-nitrobenzoyl valerolactam issubstituted for the nonanoyl valerolactam bleach activator. Thelaundering method of Example III is repeated. In the test, all fabricsdisplay significantly improved whiteness after laundering compared withfabrics which have not been exposed to the bleaching system of theinvention.

EXAMPLE VI

A granular detergent is prepared by a procedure identical to that ofExample III, with the exceptions that 5% isononanoyl valerolactam issubstituted for the nonanoyl valerolactam bleach activator and theamount of sodium percarbonate is 10%. The laundering method of ExampleIII is repeated. In the test, all fabrics display significantly improvedwhiteness after laundering compared with fabrics which have not beenexposed to the bleaching system of the invention.

EXAMPLE VII

A granular detergent is prepared by a procedure identical to that ofExample III, with the exceptions that 20% 3-chlorobenzoyl valerolactamis substituted for the nonanoyl valerolactam bleach activator and theamount of sodium percarbonate is 20%. The laundering method of ExampleIII is repeated. In the test, all fabrics display significantly improvedwhiteness after laundering compared with fabrics which have not beenexposed to the bleaching system of the invention.

EXAMPLE VIII

A granular detergent is prepared by a procedure identical to that ofExample III, with the single exception that 15% of a 1:1 mixture ofbenzoyl valerolactam and nonanoyl valerolactam is substituted for thenonanoyl valerolactam bleach activator. The laundering method of ExampleIII is repeated. In the test, all fabrics display significantly improvedwhiteness after laundering compared with fabrics which have not beenexposed to the bleaching system of the invention.

EXAMPLE IX

A granular detergent is prepared by a procedure identical to that ofExample III, with the single exception that 15% of a 1:1 mixture ofbenzoyl valerolactam and nonanoyloxybenzenesulfonate is substituted forthe nonanoyl valerolactam bleach activator. The laundering method ofExample III is repeated. In the test, all fabrics display significantlyimproved whiteness after laundering compared with fabrics which have notbeen exposed to the bleaching system of the invention.

EXAMPLE X

A granular detergent is prepared by a procedure identical to that ofExample III, with the single exception that 15% of a 1:1 mixture of4-ethylbenzoyl valerolactam and a benzoxazin-type bleach activator issubstituted for the nonanoyl valerolactam bleach activator. Thelaundering method of Example III is repeated. In the test, all fabricsdisplay significantly improved whiteness after laundering compared withfabrics which have not been exposed to the bleaching system of theinvention.

EXAMPLE XI

A granular detergent is prepared by a procedure identical to that ofExample III, with the single exception that an equivalent amount ofdecanoyl valerolactam is substituted for the nonanoyl valerolactambleach activator. The laundering method of Example III is repeated. Inthe test, all fabrics display significantly improved whiteness afterlaundering compared with fabrics which have not been exposed to thebleaching system of the invention.

EXAMPLE XII

A granular detergent composition is prepared comprising the followingingredients.

    ______________________________________    Component               Weight %    ______________________________________    Anionic alkyl sulfate   7    Nonionic surfactant     5    Zeolite A (0.1-10 micron)                            10    Trisodium citrate       2    SKS-6 silicate builder  10    Acrylate maleate polymer                            4    Nonanoyl valerolactam   10    Sodium percarbonate     25    Sodium carbonate        5    Ethylenediamine disuccinate chelant (EDDS)                            0.4    Suds suppressor         2    Enzymes*                1.5    Soil release agent      0.2    Minors, filler** and water                            Balance to 100%    ______________________________________     *1:1:1 mixture of protease, lipase, and cellulase.     **Can be selected from convenient materials such as CaCO.sub.3, talc,     clay, silicates, and the like.

An aqueous crutcher mix of heat and alkali stable components of thedetergent composition is prepared and spray-dried. The other ingredientsare admixed therewith so that they contain the ingredients tabulated atthe levels shown.

The detergent granules with bleaching system are added together with a2.7 kg load of fabrics to an automatic washing machine. Actual weightsof detergent and ester compositions are taken to provide a 5000 ppmconcentration of the detergent composition in the 17 liter (4.5 gallon)water-fill machine. The water used has 10 grains/gallon hardness and apH of 7 to 7.5 prior to (about 9 to about 10.5 after) addition of thedetergent composition.

The fabrics are laundered at 40° C. (104° F.) for a full cycle (40 min.)and rinsed at 21° C. (70° F.).

At the end of the last rinse cycle, the test swatches are dried in adryer. Tristimulus meter readings (L,a,b) are then determined for eachtest swatch. Whiteness performance in terms of Hunter Whiteness Values(W) is then calculated according to the following equation:

    W=(7L.sup.2 -40Lb)/700

The higher the value for W, the better the whiteness performance. In theabove test, fabrics exposed to the bleaching system displaysignificantly improved whiteness after laundering compared with fabricswhich have not been exposed to the bleaching system of the invention.

EXAMPLE XIII

A granular detergent is prepared by a procedure identical to that ofExample XII, with the exception that 10% isononanoyl valerolactam issubstituted for the nonanoyl valerolactam bleach activator. Thelaundering method of Example XII is repeated. In the test, all fabricsdisplay significantly improved whiteness after laundering compared withfabrics which have not been exposed to the bleaching system of theinvention.

EXAMPLE XIV

A granular detergent is prepared by a procedure identical to that ofExample XII, with the exceptions that 10% 2-ethylhexanoyl valerolactamis substituted for the nonanoyl valerolactam bleach activator. Thelaundering method of Example XII is repeated. In the test, all fabricsdisplay significantly improved whiteness after laundering compared withfabrics which have not been exposed to the bleaching system of theinvention.

EXAMPLE XV

A granular detergent is prepared by a procedure identical to that ofExample XII, with the exceptions that 15% benzoyl valerolactam issubstituted for the nonanoyl valerolactam bleach activator and theamount of sodium percarbonate is 30%. The laundering method of ExampleXII is repeated. In the test, all fabrics display significantly improvedwhiteness after laundering compared with fabrics which have not beenexposed to the bleaching system of the invention.

EXAMPLE XVI

A granular detergent is prepared by a procedure identical to that ofExample XII, with the single exception that 15% of a 1:1 mixture of4-chlorobenzoyl valerolactam and a benzoxazin-type bleach activator issubstituted for the nonanoyl valerolactam bleach activator. Thelaundering method of Example XII is repeated. In the test, all fabricsdisplay significantly improved whiteness after laundering compared withfabrics which have not been exposed to the bleaching system of theinvention.

EXAMPLE XVII

A granular detergent is prepared by a procedure identical to that ofExample XII, with the single exception that 15% of a 1:1 mixture ofisononanoyl valerolactam and tetraacetyl ethylene diamine bleachactivator is substituted for the nonanoyl valerolactam bleach activator.The laundering method of Example XII is repeated. In the test, allfabrics display significantly improved whiteness after launderingcompared with fabrics which have not been exposed to the bleachingsystem of the invention.

EXAMPLE XVIII

A granular detergent is prepared by a procedure identical to that ofExample XII, with the single exception that 15% of a 1:1 mixture ofisononanoyl valerolactam and benzoyl caprolactam is substituted for thenonanoyl valerolactam bleach activator. The laundering method of ExampleXII is repeated. In the test, all fabrics display significantly improvedwhiteness after laundering compared with fabrics which have not beenexposed to the bleaching system of the invention.

EXAMPLE XIX

A laundry bar suitable for hand-washing soiled fabrics is preparedcomprising the following ingredients.

    ______________________________________    Component            Weight %    ______________________________________    C.sub.12 linear alkyl benzene sulfonate                         30    Phosphate (as sodium tripolyphosphate)                         7    Sodium carbonate     15    Sodium pyrophosphate 7    Coconut monoethanolamide                         2    Zeolite A (0.1-10 microns)                         5    Carboxymethylcellulose                         0.2    Polyacrylate (m.w. 1400)                         0.2    Benzoyl valerolactam 6.5    Sodium percarbonate  15    Brightener, perfume  0.2    Protease             0.3    CaSO.sub.4           1    MgSO.sub.4           1    Water and Filler*    Balance to 100%    ______________________________________     *Can be selected from convenient materials such as CaCO.sub.3, talc, clay     silicates, and the like.

Detergent laundry bar is extruded in conventional soap or detergent barmaking equipment as commonly used in the art. Testing is conductedfollowing the methods used in Example IV. In the test, fabrics exposedto the bleaching system display significantly improved whiteness afterlaundering compared with fabrics which have not been exposed to thebleaching system of the invention.

EXAMPLE XX

A laundry bar is prepared by a procedure identical to that of ExampleXIX, with the two exceptions that 15% of a 1:1 mixture of benzoylvalerolactam and nonanoyl valerolactam is substituted for the benzoylvalerolactam bleach activator, and the level of sodium percarbonate isincreated to 20%. The laundering method of Example XIX is repeated. Inthe test, all fabrics display significantly improved whiteness afterlaundering compared with fabrics which have not been exposed to thebleaching system of the invention.

EXAMPLE XXI

A laundry bar is prepared by a procedure identical to that of ExampleXIX, with the two exceptions that 15% of a 1:1 mixture of isononanoylvalerolactam and 2,4-dichlorobenzoyl valerolactam is substituted for thebenzoyl valerolactam bleach activator, and the level of sodiumpercarbonate is increated to 20%. The laundering method of Example XIXis repeated. In the test, all fabrics display significantly improvedwhiteness after laundering compared with fabrics which have not beenexposed to the bleaching system of the invention.

EXAMPLE XXII

A laundry bar is prepared by a procedure identical to that of ExampleXIX, with the two exceptions that 15% of a 1:1 mixture of decanoylvalerolactam and benzoyl valerolactam is substituted for the benzoylvalerolactam bleach activator, and the level of sodium percarbonate isincreated to 20%. The laundering method of Example XIX is repeated. Inthe test, all fabrics display significantly improved whiteness afterlaundering compared with fabrics which have not been exposed to thebleaching system of the invention.

EXAMPLE XXIII

A laundry bar is prepared by a procedure identical to that of ExampleXIX, with the two exceptions that an equivalent amount of butoxybenzoylvalerolactam is substituted for the benzoyl valerolactam bleachactivator, and the level of sodium percarbonate is increated to 20%. Thelaundering method of Example XIX is repeated. In the test, all fabricsdisplay significantly improved whiteness after laundering compared withfabrics which have not been exposed to the bleaching system of theinvention.

EXAMPLE XXIV

A bleaching system is prepared comprising the following ingredients.

    ______________________________________    Component               Weight %    ______________________________________    Nonanoyl valerolactam   15    Tetraacetyl ethylene diamine                            15    Sodium percarbonate     45    Chelant (ethylenediamine disuccinate, EDDS)                            10    Filler* and water       Balance to 100%    ______________________________________     *Can be selected from convenient materials such as CaCO.sub.3, talc, clay     silicates, and the like.

Testing is conducted following the methods used in Example IV with thesingle exception that the an equivalent amount of the above bleachingsystem is substituted for the detergent composition used in Example IV.In the test, fabrics exposed to the bleaching system displaysignificantly improved whiteness after laundering compared with fabricswhich have not been exposed to the bleaching system of the invention.

EXAMPLE XXV

A bleaching system is prepared by a procedure identical to that ofExample XXIV, with the exception that an equivalent amount of4-butylbenzoyl valerolactam is substituted for the nonanoyl valerolactambleach activator. The laundering method of Example XXIV is repeated. Inthe test, all fabrics display significantly improved whiteness afterlaundering compared with fabrics which have not been exposed to thebleaching system of the invention.

EXAMPLE XXVI

A bleaching system is prepared by a procedure identical to that ofExample XXIV, with the exception that an equivalent amount ofterephthaloyl divalerolactam is substituted for the nonanoylvalerolactam bleach activator. The laundering method of Example XXIV isrepeated. In the test, all fabrics display significantly improvedwhiteness after laundering compared with fabrics which have not beenexposed to the bleaching system of the invention.

While the compositions and processes of the present invention are usefulin conventional laundering operations, it is to be understood that theyare also useful in any cleaning system which involves low water:fabricratios. One such system is disclosed in U.S. Pat. No. 4,489,455,Spendel, issued Dec. 25, 1984, which involves a washing machineapparatus which contacts fabrics with wash water containing detergentingredients using a low water: fabric ratio rather than the conventionalmethod of immersing fabrics in an aqueous bath. The compositions hereinprovide excellent bleaching performance in such mechanical systems.Typically, the ratio of water:fabric ranges from about 0.5:1 to about6:1 (liters of water:kg of fabric).

EXAMPLE XXVII

Using the machine and operating conditions disclosed in U.S. Pat. No.4,489,455, cited above, 25 grams of a composition according to ExampleIV herein are used to launder fabrics with concurrent bleaching. Ifdesired, sudsing of the composition can be minimized by incorporatingtherein from 0.2% to 2% by weight of a fatty acid, secondary alcohol, orsilicone suds controlling ingredient. In the test, all fabrics displaysignificantly improved whiteness after laundering compared with fabricswhich have not been exposed to the bleaching system of the invention.

The valerolactam bleach activators are preferably not absorbed onto theperoxygen bleaching compound. To do so in the presence of other organicdetergent ingredients could cause safety problems. It has now beendiscovered that the acyl valerolactam bleach activators of thisinvention can be dry-mixed with peroxygen bleaching compounds,especially perborate and percarbonate, and thereby avoid potentialsafety problems. If the valerolactam is a liquid, before dry-mixing, itcan be formed into a suitable "particle" using conventional means knownin the art.

EXAMPLE XXVIII

A laundry bar suitable for hand-washing soiled fabrics is preparedcomprising the following ingredients.

    ______________________________________    Component            Weight %    ______________________________________    Linear alkyl benzene sulfonate                         30    Phosphate (as sodium tripolyphosphate)                         7    Sodium carbonate     20    Sodium pyrophosphate 7    Coconut monoethanolamide                         2    Zeolite A (0.1-10 microns)                         5    Carboxymethylcellulose                         0.2    Polyacrylate (m.w. 1400)                         0.2    Isononanoyl valerolactam                         5    Sodium perborate tetrahydrate                         10    Brightener, perfume  0.2    Protease             0.3    CaSO.sub.4           1    MgSO.sub.4           1    Water                4    Filler*              Balance to 100%    ______________________________________     *Can be selected from convenient materials such as CaCO.sub.3, talc, clay     silicates, and the like.

A detergent laundry bar is extruded in conventional soap or detergentbar making equipment as commonly used in the art with the bleachingactivator dry-mixed with the perborate bleaching compound and notaffixed to the surface of the perborate. Testing is conducted followingthe methods used in Example IV. In the test, fabrics exposed to thebleaching system display significantly improved whiteness afterlaundering compared with fabrics which have not been exposed to thebleaching system of the invention.

EXAMPLE XXIX

A granular detergent composition is prepared comprising the followingingredients.

    ______________________________________    Component               Weight %    ______________________________________    Linear alkyl benzene sulfonate                            20    Phosphate (as sodium tripolyphosphate)                            20    Sodium carbonate        10    Sodium silicate         3    Sodium perborate tetrahydrate                            20    Ethylenediamine disuccinate chelant (EDDS)                            0.4    Sodium sulfate          5.5    4-nitrobenzoyl valerolactam                            5    Nonanoyloxybenzenesulfonate                            5    Minors, filler** and water                            Balance to 100%    ______________________________________     **Can be selected from convenient materials such as CaCO.sub.3, talc,     clay, silicates, and the like.

Aqueous crutcher mixes of heat and alkali stable components of thedetergent compositions are prepared and spray-dried and the otheringredients are dry-mixed so that they contain the ingredients tabulatedat the levels shown.

Testing is conducted following the methods used in Example V. In thetest, fabrics exposed to the bleaching system display significantlyimproved whiteness after laundering compared with fabrics which have notbeen exposed to the bleaching system of the invention.

EXAMPLE XXX

This Example illustrates several liquid bleach compositions inaccordance with the invention, all of which are made by the generalprocess described hereinafter. The desired amount of a chelating agentis added to a beaker of water, after which the resulting solution isstirred until the chelating agent is completely dissolved. A phasestabilizer is added to the solution while it is being continuouslystirred. Thereafter, the bleach activator and optionally an additionalchelating agent is dissolved in the solution. The pH of the solution isadjusted to about 4.0 with an alkaline adjusting agent such as sodiumhydroxide.

The following translucent, stable aqueous liquid bleach compositions(Samples A-F) are made as described above, all amounts being expressedas percentages by weight.

                  TABLE I    ______________________________________    Samples           A     B       C       D     E     F    ______________________________________    Water    81.28   81.86   82.44 83.02 78.60 83.98    NEODOL   10.00   10.00   10.00 10.00 10.00 10.00    91-10.sup.1    Dipicolinic             0.05    0.05    0.05  0.05  0.05  0.05    Acid.sup.2    DEQUEST  0.05    0.05    0.05  0.05  0.05  0.05    2010.sup.3    Nonanoyl 5.80    5.80    5.80  5.80  7.71  3.87    Valerolactam    Citric Acid             0.50    0.50    0.50  0.50  0.50  0.50    NaOH     to pH4  to pH4  to pH4                                   to pH4                                         to pH4                                               to pH4    Hydrogen 2.32    1.74    1.16  0.58  3.09  1.55    Peroxide    ______________________________________     .sup.1 Alkyl ethoxylate available from The Shell Oil Company.     .sup.2 2,6Pyridine dicarboxylic acid commercially available from Aldrich     Chemical Co.     .sup.3 Hydroxyethylidene diphosphonic acid commercially available from     Monsanto Co.

What is claimed is:
 1. An acyl valerolactam bleach activator of theformula: ##STR12## wherein R², R³, R⁴, R⁵, and R⁶ are members selectedfrom the group consisting of H, halogen, except for chlorine, alkyl,alkoxy, alkoxyaryl, alkaryl, and alkaryloxy moieties containing fromabout 1 to about 12 carbon atoms, and substituents having thestructures: ##STR13## wherein R⁷ is selected from the group consistingof H, a C₂ or higher alkyl, alkaryl, alkoxy, alkoxyaryl, alkaryloxy, andaminoalkyl; X is O, NH, or NR⁹, wherein R⁹ is H or a C₁ -C₄ alkyl group;and R⁸ is an alkyl, cycloalkyl, or aryl group containing from 3 to 11carbon atoms; provided that R², R³, R⁴, R⁵, and R⁶ are not all H.
 2. Alaundry bleaching system comprising:i) at least about 0.1% by weight ofa peroxygen bleaching compound; and ii) at least about 0.1% by weight ofan acyl valerolactam bleach activator of the formulae: a) ##STR14##wherein R¹ is a substituted or unsubstituted alkyl or alkoxy groupcontaining from about 1 to about 18 carbon atoms wherein the longestlinear alkyl or alkoxy chain extending from and including the carbonylcarbon contains from about 2 to about 12 carbon atoms; b) ##STR15##wherein R², R³, R⁴, R⁵, and R⁶ are members selected from the groupconsisting of H, halogen, nitro, alkyl, alkoxy, alkoxyaryl, alkaryl, andalkaryloxy moieties containing from about 1 to about 12 carbon atoms,and substituents having the structures; ##STR16## wherein R⁷ is selectedfrom the group consisting of H, alkyl, alkaryl, alkoxy, alkoxyaryl,alkaryloxy, and aminoalkyl; X is O, NH, or NR⁹, wherein R⁹ is H or a C₁-C₄ alkyl group; and R⁸ is an alkyl, cycloalkyl, or aryl groupcontaining from 3 to 11 carbon atoms; or c) mixtures of a) and b);wherein the weight ratio of bleach activator to peroxygen bleachingcompound ranges from about 2:1to about 1:5.
 3. A bleaching systemaccording to claim 2 wherein said peroxygen bleaching compound ispercarbonate or perborate and said valerolactam activator is selectedfrom the group consisting of benzoyl valerolactam, isononanoylvalerolactam, 2-ethylhexanoyl valerolactam, 3-chlorobenzoylvalerolactam, 4-nitrobenzoyl valerolactam, dodecanoyl valerolactam,decanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam,2-ethylhexanoyl valerolactam, 4-butoxybenzoyl valerolactam,4-ethoxybenzoyl valerolactam, 4-ethylbenzoyl valerolactam, and mixturesthereof.
 4. A laundry detergent composition comprising at least about0.1% of the bleaching system according to claim 2 and at least about 1%by weight of conventional detergent ingredients.
 5. A laundry detergentcomposition according to claim 4 wherein said conventional detergentingredients comprise a protease enzyme.
 6. A composition according toclaim 4 wherein said conventional detergent ingredients comprise fromabout 5% to about 80% of a detersive surfactant; said peroxygenbleaching compound is percarbonate or perborate.
 7. A compositionaccording to claim 6 further comprising from 0% to about 15% of a secondbleach activator selected from the group consisting of tetraacetylethylene diamine, alkanoyloxybenzenesulfonate, benzoxazin-typeactivators, peroxyacid activators having amide moieties. N-acylcaprolactams and mixtures thereof.
 8. A composition according to claim 7wherein R¹ is selected from the group consisting of n-heptyl, n-nonyl,n-decyl, n-undecyl, decenyl, 2,4,4-trimethylpentyl, 1-ethylpentyl, andmixtures thereof; and the second bleach activator is tetraacetylethylene diamine.
 9. A composition according to claim 7 wherein R², R³,R⁴, and R⁵ are H and R⁶ is selected from the group consisting of H,methyl, methoxy, ethyl, ethoxy, n-propyl, n-propoxy, isopropyl,isopropoxy, n-butyl, tert-butyl, n-butoxy, tert-butoxy, n-pentyl,n-pentoxy, n-hexyl, n-hexoxy, --Cl, and --NO₂ ; and the second bleachactivator is tetraacetyl ethylene diamine.
 10. A method for cleaningfabrics in automatic washing machines having parts made of naturalrubber which is susceptible to oxidative degradation, said methodcomprising agitating said fabrics in said machine in an aqueous liquorcomprising a bleaching system according to claim 2 such that saidnatural rubber parts of said machine are substantially undamaged by thebleaching system.
 11. A method for cleaning fabrics, said methodcomprising contacting said fabrics in an aqueous liquor comprising ableaching system which comprises an effective amount of a compositioncomprising:a) at least about 0.1% by weight of a peroxygen bleachingcompound capable of yielding hydrogen peroxide in an aqueous solution;and b) at least about 0.1% by weight of one or more acyl valerolactambleach activators having the formulae:a) ##STR17## wherein R¹ is asubstituted or unsubstituted alkyl or alkoxy group containing from about1 to about 18 carbon atoms wherein the longest linear alkyl or alkoxychain extending from and including the carbonyl carbon contains fromabout 2 to about 12 carbon atoms; b) ##STR18## wherein R², R³, R⁴, R⁵,and R⁶ are members selected from the group consisting of H, halogen,nitro, alkyl, alkoxy, alkoxyaryl, alkaryl, and alkaryloxy moietiescontaining from about 1 to about 12 carbon atoms, and substituentshaving the structures: ##STR19## wherein R⁷ is selected from the groupconsisting of H, alkyl, alkaryl, alkoxy, alkoxyaryl, alkaryloxy, andaminoalkyl; X is O, NH, or NR⁹, wherein R⁹ is H or a C₁ -C₄ alkyl group;and R⁸ is an alkyl, cycloalkyl, or aryl group containing from 3 to 11carbon atoms; or c) mixtures of a) and b);wherein the weight ratio ofbleach activator to peroxygen bleaching compound ranges from about 2:1to about 1:5.
 12. A method according to claim 11 wherein the peroxygenbleaching compound is selected from the group consisting of sodiumperborate monohydrate, sodium perborate tetrahydrate, sodiumpyrophosphate peroxyhydrate, urea peroxyhydrate, sodium percarbonate,sodium peroxide and mixtures thereof.
 13. A method according to claim 12wherein said bleach system further comprises from 0% to about 15% of asecond bleach activator.
 14. A method according to claim 13 wherein saidsecond bleach activator is selected from the group consisting ofalkanoyloxybenzenesulfonate, tetraacetyl ethylene diamine,benzoxazin-type activators, peroxyacid activators having an amidemoiety, N-acyl caprolactams and mixtures thereof.
 15. A liquid bleachcomposition comprising:a) from about 1% to about 25% by weight of ableach activator having the formulae:a) ##STR20## wherein R¹ is asubstituted or unsubstituted alkyl or alkoxy group containing from about1 to about 18 carbon atoms wherein the longest linear alkyl or alkoxychain extending from and including the carbonyl carbon contains fromabout 2 to about 12 carbon atoms; b) ##STR21## wherein R², R³, R⁴, R⁵,and R⁶ are members selected from the group consisting of H, halogen,nitro, alkyl, alkoxy, alkoxyaryl, alkaryl, and alkaryloxy moietiescontaining from about 1 to about 12 carbon atoms, and substituentshaving the structures: ##STR22## wherein R⁷ is selected from the groupconsisting of H, alkyl, alkaryl, alkoxy, alkoxyaryl, alkaryloxy, andaminoalkyl; X is O, NH, or NR⁹, wherein R⁹ is H or a C₁ -C₄ alkyl group;and R⁸ is an alkyl, cycloalkyl, or aryl group containing from 3 to 11carbon atoms; or c) mixtures of a) and b); and b) from about 0.1% toabout 10% by weight of a peroxygen bleaching compound comprisinghydrogen peroxide or which is capable of yielding hydrogen peroxide inan aqueous solution.
 16. A liquid bleach composition according to claim15 further comprising from about 1% to about 20% of a nonionicsurfactant phase stabilizer.